Petroleum resins by after-treatment with diolefins



nitcd States Patent PETROLEUlVI RESINS BY AFTER-TREATMENT WITH DIOLEFINS Stanley B. Mirviss, Roselle, and Fred W. Banes, Westfield, N. J., assignors to Esso Research and EngineeringCompany, a corporation of Delaware No Drawing. Application December 31, 1952, Serial No. 329,104

9 Claims. (Cl. 260-455) jugated G to s alicycliciarrdrbranched chain aliphatic diole'fins, specifically iisoprene, .ora .cyclic .diolefin .such as .cyclopentadiene, or methylcyclopentadiene, or mixtures thereof is addedtolhe reaction grnixture,'improved ;resin-yields-are obtained-and theresin yieldsso Obtained havehigherrsoiftening .points than a are realized when the diolefins are not added to the "reaction mixture. The

-resin-products are substantially soluble,'that'is, they contain substantially no insoluble gel. In order toachieve these improved eifects, .it.is necessary and criticalthat theiliolefinbe added 'tothe reaction mixtureafter the major portion 'or all of ithealuminum halide catalyst has been 'added. If the diole'fin material in concentrations ;greater:th-an:-about3315'wt. p.ercent is added to or is pres- 'ent-'in;the reaction mixture initially as part of theentire hydrocarbon feed, inferior yields are insoluble, gel-con- 'taining-proiluctsareobtained.

I-Iydroca'rbon resins'to'which the present invention is applicable are made by treating a hydrocarbon mixture containing diolefins, olefins, aromatics, 'parafiins, .and naphthenes with 0.25% to 2.0% based on the unsaturated hydrocarbon feed of an aluminum 'halidecat-alyst such as aluminum chloride and aluminum bromide. The catalysts may be used as solids or theyrnay be employed as solutions, slurries or complexes. )HYdrocatbOnycomplexes of the catalysts, obtained.byreaction-ofthe aluminum halide with a resin raflinate; for example one containing about 60% olefins and 40% aromatics, ;are also quite useful.

Typical hydrocarbon fractions useful forfceidsdn making these resins boil from 20 to 170 C. Analyses show the following composition: Distillation range:

Fractions, C.-- Weight ,percent -'Ihe'hydrocarbon stream used as .ffeed stocks should "be one from which substantially all the isoprene-contain- 2 ing 'cut'has'been removed, since'the presence of'this'total .cut during polymerization increases the amountmfmndesirable liquid polymerproduct.

'The polymerization reactions 'are conducted at temerably from -15 to +60 C. Residual catalyst is quenched 'by suitable methods, such QSZEld'dltlOHt'O'fl'IlthYl alcohol and -:subseguentfiltration-or by 'water and/or caustic washing. The final vsolut-ion is then stripped of unreacted hydrocarbons -and low molecular weight oils by vacuum or steam distillation. Aihydrocarbon mixture suitable for resin production 'is conveniently "found .in seleetedhydroca'rbon streams.obtainedbyesteam.cracking gas oils. These cracked streams ha-ve 'boiling ranges between 20 tend 517.0 .C.., tor-away :be (composed 19f rany inter-mediate fraction vselected :from :this :range.

:The,invention .eonsistsiofiaddingztoztherreactionmixture after substantially all of the catalyst 'has been :added, only minor quantities -ofa diolefin or cyclic diolefin. When the reactions are carried out at 0 C. or lower, it

i isadesirahleitozdilute the l'IfiCilOll'cfIliXfiiIZCM/lth "an inert :diluent 'as. III-hexane 'Pil'Ol :to tthe; addition .of :the :motlifying diolefins. The diolefins most satisfactory for use are included in the class of conjugated C5 and Cs alicyclic and branched chain aliphatic diolefins. Mixtures of these 'materials-may-also be used. The quantity of diolefin or cyclic diolefin added to obtain the herein described improved properties and yield of the resin, depends some- What on the composition of the original polymerization feed stream. Generally, from 5% to 20% of isoprene, cyclopentadiene ;or methylcyclopentadiene, based on the total;naphtha and diolefins, is added. It is preferable to limit the cyclopentadiene concentration to 20% or less on the total feed since higher concentrations give highly reactive products which tend to cross-link when subjected "to verylhighlemperature stripping or resin molding operations. If ,desired,.the modified resins .carnbe, thermally 'botlie'dto give resins of'further'improved, softening point.

"Furthermore, this thermal bodying treatment is much .milderthanthat usually employed-ltoheat'bo'cly, petroleum resins to increase the "softening ,point. 35% is-usually necessaryto achieve the desiredjimprove- -ments.

A .niinimum of The-polymerization to ,prepare the resin is necessarily carried out inbatch operation or "in separate stages or continuouslywtith the modifying diolefin or cyclic diolefin being added after the first stageof polymerization -.when substantially all the catalyst has been added. The :reaction mixture containing the -motiifying "diolefin is agitated at- 'the initial, or .even a slightly igherreaction temperature, until the polymerization reaction is essentlallyl complete.

.=A isteam.crackedtdistillate boiling largely-in the range .of .40.to.145".C-andcontainingabout 8% diolefins, 30%

aromatics, 60% olefins andr2% paraffins'andnnaphthenes was ,pnlymerized with .solid .AlClsqor: slurries of :powdered AlCls vvin..11:hexane. In 1fl$fiCS .of ,runs, 1% .-A1Cl3 was .employed;.the catalystbeing added to .the reactor tover aa /2 :to .34 ;-hour,p.eriod. The temperature .was maintained at .20-25 .C. .during the time .of catalyst .-addition :as Well as for:.an.additional /s to .hounreactiomperiod following the catalyst addition. The reaction mixtures were quenched With 5% H2SO4"S0ll.1tlOIl (aqueous) and then water washed. .Finally, .the .washed resin-solutions were stripped ,to a tresin temperature :of ..*26.0-.28.0 C. :at 5-6 mm. .I-Ig .to :recover shard tresinous ,products.

Various quantities of isoprene were added to the naphthaboth before and after the catalyst addition as noted 49% olefins and 1% paraffins and naphthenes. Polyin the following Table I showing the data obtained. merizations were carried out using 1% AlCla on the Table 1 Weight Percent on Weight Percent Total Feed on Feed Pmpemes Time of Isoprene N Mb I Addition R llnsialuble ioft C I I Iodine up 8 SOPXBDG 65111 O YlIlel' O O! (G 61) no. Number a 100 19.7 None 88 5 197 90 Before A1013. 29. 8 2. 0 91 a 182 85 Before A101: 32.6 4. 3 91 3 171 90 10 After A1013" 34. 0 None 92 4 169 85 15 After A101; 36. 8 None 96 3 1 Ring and ball method (ASTM E-2851T). 1 Color of a solution of 1 g. resin per 67 ml. xylenes compared to Gardner color index. a AS'IM D-555-47.

These data show the advantage of adding the aliphatic hydrocarbon feed, the catalyst being used both as the diolefin after the catalyst; namely, that increased yields powdered material and as a 10% slurry in n-hexane. The

of completely soluble and higher softening point resin reaction time and temperature and product work-up were products are obtained. substantially the same as described above in Example 1. EXAMPLE 2 In these runs cyclopentadiene and methylcyclopentadiene monomers were added to the reactor both before A series of resins was prepared from a steam cracked and after completion of the catalyst addition to the basic distillate boiling in the range of about to 135 C. and reaction feed mixture.

Table III Wt. Percent on Total Feed Wt. Gel For Resin Properties Time of CyclodleentYield motion olefin Add'n of Solu- During Soft Iodine Naphtha CPD 1 MCPD ble Resin Run Pt 0 Color Number 100 30.8 No 79 3 221 1 9s 2 Before A101; 23.3 Yes... 89 3 228 90 10 Before A101; 34. 6 Ya.-. 95 90 1o Before A101; 39.0 Yes- 103 95 5 After A101; 31.6 No 95 9o 10 After A101: 33.8 1\o 99 3 257 l Cyelopentadiene monomer. 7 Methylcyclopentadiene monomer. containing about 15% diolefins, 24% aromatics, 60% ole- These data show that cyclodiolefin concentrations as fins and 1% parafiins and naphthenes. The procedure for low as 2% result in the formation of some insoluble resin preparing and working up the resinous products were the product when the polymerization is carried out with same as described in Example 1. In these runs, carried AlCl3. When added after the catalyst, equally good yields out at 25 C., both 1% and 2% A1Cl3 concentrations of high softening point resins are obtained without gel were employed, as noted in the following Table II, and formation. The data show that the addition of cyclovarying quantities of cyclic and acyclic diolefins were pentadiene monomer results in somewhat higher yields added to the naphtha stream described above. of resins but in both cases undesirable insoluble product Table II Weight Percent Wt. Percent on Total Feed on Hydrocarbon Resin Properties 2 5?" Time of nioienn Feed A101 Addn s it I din 0 0 8 Naphtha Isoprene MCJPD Resin Gel PtHOQ Color Number 100 32 2 None 90 8 192 90 10 1 0 Before AlOh... a9 4 4.1 93 4 no 10 2 0 Before A101; 4o. 5 4.3 95 5 as 15 1.0 Before A101: 38.1 10.3 97 4 168 so 10 1. 0 After A1Ch-.-- 42. 7 None 97 2 85 15 2.0 After A1o1r- 47 5 None 98 3 93.5 6 5 1 0 After AlCl|.. 36 7 None 112 4 202 1 Methylcyelopentadiene monomer.

These data further show that isoprene and cyclopentais produced when the monomers are present in the initial diene monomers can be employed to improve substanfeed. tially both the resin yields and softening points without EXAMPLE 4 encountering insoluble polymer formation. These data A naphtha feed stream boiling in the range of 20 to further show that these monomers must be added after 140 C. and containing about 18% diolefins, 20% arothe catalyst in order to achieve these desired results. matics, 60% olefins and 2% paraffins and naphthenes was EXAMPLE 3 employed in another series of runs. The reactions were carried out at 2025 C. with 1% catalyst being added In another series of experiments, a naphtha feed was to the hydrocarbon feed over a /2 hour period. The time employed which boiled in the range of 35 to 140 C. and of isoprene addition was varied as was the type of catalyst which contained about 14% diolefins, 36% aromatics, employed in the runs. After completion of the catalyst ewe-saws 6 QWhatis claimed is: 1. A process -for improving "the quality and -yield of. unsaturated polymerized olefin-diolefin hydrocarbon resins "which comprises t-reat-ing :a "solution of "previously poly- -'5 merized unsaturated hydrocarbon --resin'before quenchaddition-and the addition of isoprene "(if 'any), the reaction mixture masiagitated at 245* iQffonan additional .nne hour. .At the end,.,of.this.time,-,the reaction mixture .was water .washed thoroughly and then,;stripped;to :ayhot- Itoms temperature of 260 C...at,3-:5. Hg.

Table IV gzf g j Wt. Percent Yield Resin Properties Catalyst T111162; (Iisgprene Naphtha Isoprene Resin Gel gg g Color 100 AlChm. 32.1--.. 90 3 95 AlCl;- BeforeAlCl 38.41" 1 90 3 80 AlBl's.-. Before AlBr; Low 80 20 AlBr; After AlBrg 49.4. 99 3 EXAMPLE 5 ing and removal of catalyst residues with from 5% In still another series of polymerizations a naphtha feed stream was used which boiled in the range of about 35 to 135 C. The composition of the naphtha stream used was essentially the same as that described in Exto 20% by weight, based on the final total amount of polymerization feed, of a hydrocarbon selected from the class consisting of C5 to Cs conjugated diolefins and cyclic diolefin.

2. A process according to claim 1 in which the cyclic ample 2. In each run the catalyst was added over a /2 diolefin is a conjugated C5 to C6 alicyclic diolefin. hour period at the temperature shown in Table V and the 3. Process according to claim 1 in which the catalyst is reaction mixture was then agitated at this temperature for aluminum chloride; the hydrocarbon being isoprene. an additional hour. In certain cases additions of cyclic 4. A process according to that of claim 2 in which or acyclic diolefins were made after completion of the the diolefin is cyclopentadiene. catalyst addition and at the beginning of or during the 5. A process according to that of claim 2 in which final period of agitation. the diolefin is methylcyclopentadiene.

Table V Weight Percent on Total Feed Percent Resin Properties Yield Reaction Wt.

Time of Diolefln Temp., Percent Addition 0. A10]: so Naphtha Isoprene CPD MOPD Resin Gel Pt Color 100 20-25 1.0 35.6 None 87 2 s0 20 60 0.5 Before AlOl. 47.2 12.0 101 2 00 10 0 2.0 After A101,"-.- 48.1 None 90 2 s0 20 50-55 0.5 After A1013-.. 49.2 None 102 2 s0 50-55 0.5 After A1013"--- 48.9 None 145 9 s5 30 1.5 After AlOie 49.4 None 145 0 85 15 t 1. 5 After AlDl; 45. 8 None 148 9 1 cyclopentadiene. 1 Methyl cyclopentadiene. AlBn used as catalyst.

t Diluted with vol. percent n-hexane based on originai teed after catalyst addition and prior to diolefin addition.

These data show that by adding cyclodiolefins or isoprene to polymerizations after the catalyst, a large improvement in resin yields and softening point can be realized without also encountering undesirable gel formation. The invention is applicable over wide temperature ranges using both AlCl3 and AlBra as catalyst at concentrations as high as 2% on the hydrocarbon feed.

EXAMPLE 6 A naphtha stream boiling largely in the range of 70 to 170 C. (10% below 70 C.) and containing about 15% diolefins, 40% aromatics and olefins was polymerized with 1% AlCls at 25 C. and gave a 16.2% yield of a resin having a softening point of 80 C. This naphtha was subject to a large improvement with respect to resin yield and softening point by the addition of 10% of either isoprene or cyclopentadiene to the reaction mixture after completion of the catalyst addition. On the other hand, a naphtha of similar composition but boiling in the range of 170 to 260 gave a 25.5% yield of 110 C. softening point resin when treated with 1% AlCls at 25 C. The resin yield and softening point in this case are at desirably high levels and do not require the additions of modifying diolefins to produce usable products.

6. A catalytic process for raising the softening point and yield of an unsaturated polymerized olefin-diolefin hydrocarbon petroleum resin which comprises reacting with said resin polymerization reaction mixture at a temperature not exceeding about +75 C. and prior to completion of the polymerization reaction from 5% to 20%, based on the final total amount of polymerization feed, of a diolefin selected from the group consisting of an aliphatic branched chain C5 to Cs conjugated diolefin and a cyclic diolefin, and subsequently removing the catalyst from the resin formed.

7. A process according to that of claim 6 in which the diolefin is isoprene.

8. In a process for raising the softening point and yield of an unsaturated polymerized olefin-diolefin hydrocarbon resin obtained by polymerizing a steam cracked petroleum distillate boiling in the range of about 20 to C. in the presence of 0.25 to 2.0% of an aluminum halide catalyst at a temperature of 30 to +75 C., the improvement which comprises adding at a temperature not exceeding about +75 C. from 5% to 20%, based on the final total amount of polymerization feed, of a hydrocarbon chosen from the class consisting of C5 to C6 conjugated diolefins and cyclic diolefin having from 5 to 6 carbon atoms to at least a partially polymerized reaction mixture of said resin after addition of the catalyst is substantially completed but before removal of said catalyst.

9. Process according to claim 8 in which the polymerization temperature is between about -15 C. to +60 C., 5 the hydrocarbon being cyclopentadiene.

References Cited in the file of this patent UNITED STATES PATENTS Mue1ler-Cunradieta1. Nov. 14, 1939 Guss et a1 Nov. 13, 1945 Gleason et al July 5, 1949 McKay et al. Jan. 4, 1955 

1. A PROCESS FOR IMPROVING THE QUALITY AND YIELD OF UNSATURATED POLYMERIZED OLEFIN-DIOLEFIN HYDROCARBON RESINS WHICH COMPRISES TREATING A SOLUTION OF PREVIOUSLY POLYMERIZED UNSATURATED HYDROCARBON RESIN BEFORE QUENCHING AND REMOVAL OF CATALYST RESIDUES WITH FROM 5% TO 20% BY WEIGHT, BASED ON THE FINAL TOTAL AMOUNT OF POLYMERIZATION FEED, OF A HYDROCARBON SELECTED FROM THE CLASS CONSISTING OF C5 TO C6 CONJUGATED DIOLEFINS AND CYCLIC DIOLEFIN. 